An association and Wilson activity coefficient model for solubilities of aromatic solid pollutants in supercritical carbon dioxide

The solubilities of various solid pollutants in supercritical carbon dioxide were investigated. The intermolecular interactions play a significant role in determining the solubilities of solids in supercritical carbon dioxide. A new model equation was derived by using the concepts of association and activity coefficient model to correlate the solubilities of solids. The model equation combines the association and Wilson activity coefficient models and includes the interaction potentials between the molecules, which are useful in understanding the behavior of the solid solutes in SCCO2. The new model equation involves five adjustable parameters to correlate the solubilities of solids by incorporating the interactions between the molecules. The equation correlated 75 solid systems with an average AARD of around 9%, which was better than the correlations obtained from standard models such as Mendez Santiago-Teja (MT) model and association model. (C) 2012 Elsevier B.V. All rights reserved.

Surrogate based design optimisation of composite aerofoil cross-section for helicopter vibration reduction

Design optimisation of a helicopter rotor blade is performed. The objective is to reduce helicopter vibration and constraints are put on frequencies and aeroelastic stability. The ply angles of the D-spar and skin of the composite rotor blade with NACA 0015 aerofoil section are considered as design variables. Polynomial response surfaces and space filling experimental designs are used to generate surrogate models of the objective function with respect to cross-section properties. The stacking sequence corresponding to the optimal cross-section is found using a real-coded genetic algorithm. Ply angle discretisation of 1 degrees, 15 degrees, 30 degrees and 45 degrees are used. The mean value of the objective function is used to find the optimal blade designs and the resulting designs are tested for variance. The optimal designs show a vibration reduction of 26% to 33% from the baseline design. A substantial reduction in vibration and an aeroelastically stable blade is obtained even after accounting for composite material uncertainty.

An approach to chiral amino acids via reductive amination of ketones: hydride reduction of 1-(S)-phenethyl amine derived Schiff bases of C-protected alpha-keto acids

Various 1-acyl-2,4,10-trioxaadamantanes were prepared from the corresponding 1-methoxycarbonyl derivatives, via conversion to the N-acylpiperidine derivatives followed by reaction with a Grignard reagent in refluxing THF. These alpha-keto orthoformates were converted to the corresponding imines with 1-(S)-phenethyl amine (TiCl4/Et3N/toluene/reflux), with the Schiff bases being reduced further with NaBH4 (MeOH/0 degrees C) into the corresponding 1-(S)-phenethyl amines (diastereomeric excess 91:9 by NMR). Hydrogenolysis of the phenethyl group (Pd-C/MeOH) finally led to the 1-(aminoalkyl)trioxaadamantanes, which are chiral C-protected alpha-amino acids, in excellent overall yields. (C) 2012 Elsevier Ltd. All rights reserved.

VAM applied to dimensional reduction of non-linear hyperelastic plates

This work aims at dimensional reduction of non-linear isotropic hyperelastic plates in an asymptotically accurate manner. The problem is both geometrically and materially non-linear. The geometric non-linearity is handled by allowing for finite deformations and generalized warping while the material non-linearity is incorporated through hyperelastic material model. The development, based on the Variational Asymptotic Method (VAM) with moderate strains and very small thickness to shortest wavelength of the deformation along the plate reference surface as small parameters, begins with three-dimensional (3-D) non-linear elasticity and mathematically splits the analysis into a one-dimensional (1-D) through-the-thickness analysis and a two-dimensional (2-D) plate analysis. Major contributions of this paper are derivation of closed-form analytical expressions for warping functions and stiffness coefficients and a set of recovery relations to express approximately the 3-D displacement, strain and stress fields. Consistent with the 2-D non-linear constitutive laws, 2-D plate theory and corresponding finite element program have been developed. Validation of present theory is carried out with a standard test case and the results match well. Distributions of 3-D results are provided for another test case. (c) 2012 Elsevier Ltd. All rights reserved.

Cumulus clouds and convective boundary layers: a tropical perspective on two turbulent shear flows

This paper is a review prepared for the second Marseille Colloquium on the mechanics of turbulence, held in 2011, 50 years after the first. The review covers recent developments in our understanding of the large-scale dynamics of cumulus cloud flows and of the atmospheric boundary layer in the low-wind convective regime that is often encountered in the tropics. It has recently been shown that a variety of cumulus cloud forms and life cycles can be experimentally realized in the laboratory, with the transient diabatic plume taken as the flow model for a cumulus cloud. The plume is subjected to diabatic heating scaled to be dynamically similar to heat release from phase changes in clouds. The experiments are complemented by exact numerical solutions of the Navier-Stokes-Boussinesq equations for plumes with scaled off-source heating. The results show that the Taylor entrainment coefficient first increases with heating, reaches a positive maximum and then drops rapidly to zero or even negative values. This reduction in entrainment is a consequence of structural changes in the flow, smoothing out the convoluted boundaries in the non-diabatic plume, including the tongues engulfing the ambient flow. This is accompanied by a greater degree of mixedness in the core flow because of lower dilution by the ambient fluid. The cloud forms generated depend strongly on the history of the diabatic heating profile in the vertical direction. The striking effects of heating on the flow are attributable to the operation of the baroclinic torque due to the temperature field. The mean baroclinic torque is shown to peak around a quasi-cylindrical sheet situated midway between the axis of the flow and the edges. This torque is shear-enhancing and folds down the engulfment tongues. The increase in mixedness can be traced to an explosive growth in the enstrophy, triggered by a strong fluctuating baroclinic torque that acts as a source, especially at the higher wave numbers, thus enhancing the mixedness. In convective boundary layers field measurements show that, under conditions prevailing in the tropics, the eddy fluxes of momentum and energy do not follow the Monin-Obukhov similarity. Instead, the eddy momentum flux is found to be linear in the wind speed at low winds; and the eddy heat flux is, to a first approximation, governed by free convection laws, with wind acting as a small perturbation on a regime of free convection. A new boundary layer code, based on heat flux scaling rather than wall-stress scaling, shows promising improvements in predictive skills of a general circulation model.

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Thermoelectric properties of Bi-added Co4Sb12 skutterudites

Void filling in (I) Bi-x-added Co4Sb12 or (II) Sb/Bi substitution of Co4Sb12-xBix has been investigated for structural and thermoelectric properties evaluation. X-ray powder data Rietveld refinements combined with electron probe microanalyses showed a polycrystalline and practically Bi-free CoSb3 skutterudite phase as the major constituent as well as a secondary Bi phase in the grain boundaries. For series I alloys, the electrical conductivity, Seebeck coefficient and thermal conductivity were measured as a function of temperature in the range from 450 to 750 K. The electrical conductivity of all the samples increased with increasing temperature, showing a semiconducting nature with smaller values of the Seebeck coefficient for higher Bi fractions. Conduction over the entire temperature range was found to arise from a single p-type carrier. Thermal conductivity showed a reduction with Bi added in all the samples, except for Bi0.75Co4Sb12, and the lowest lattice thermal conductivity was found for a Bi-added fraction of 0.5. The maximum zT value of 0.53 at 632 K is higher than that of Co4Sb12.

Accelerating Reduction for Enabling Fast Multiplication over Large Binary Fields

In this paper we present a hardware-software hybrid technique for modular multiplication over large binary fields. The technique involves application of Karatsuba-Ofman algorithm for polynomial multiplication and a novel technique for reduction. The proposed reduction technique is based on the popular repeated multiplication technique and Barrett reduction. We propose a new design of a parallel polynomial multiplier that serves as a hardware accelerator for large field multiplications. We show that the proposed reduction technique, accelerated using the modified polynomial multiplier, achieves significantly higher performance compared to a purely software technique and other hybrid techniques. We also show that the hybrid accelerated approach to modular field multiplication is significantly faster than the Montgomery algorithm based integrated multiplication approach.

Performance and reliability of Gd2O3 and stacked Gd2O3-Eu2O3 metal-insulator-metal capacitors

Gd2O3-based metal-insulator-metal capacitors have been characterized with single layer (Gd2O3) and bilayer (Gd2O3/Eu2O3 and Eu2O3/Gd2O3) stacks for analog and DRAM applications. Although single layer Gd2O3 capacitors provide highest capacitance density (15 fF/mu m(2)), they suffer from high leakage current density, poor capacitance density-voltage linearity, and reliability. The stacked dielectrics help to reduce leakage current density (1.2x10(-5) A/cm(2) and 2.7 x 10(-5) A/cm(2) for Gd2O3/Eu2O3 and Eu2O3/Gd2O3, respectively, at -1 V), improve quadratic voltage coefficient of capacitance (331 ppm/V-2 and 374 ppm/V-2 for Gd2O3/Eu2O3 and Eu2O3/Gd2O3, respectively, at 1 MHz), and improve reliability, with a marginal reduction in capacitance density. This is attributed to lower trap heights as determined from Poole-Frenkel conduction mechanism, and lower defect density as determined from electrode polarization model.

Morphology dependent oxygen reduction activity of titanium carbide: bulk vs. nanowires

Titanium carbide (TiC) possesses fascinating properties like high electrical conductivity and high mechanical strength coupled with high corrosion resistance and stability in acidic and alkaline environments. The present study demonstrates the tunability of mechanistic aspects of oxygen reduction reaction (ORR) using TiC nanostructures. One dimensional TiC nanostructures (TiC-NW) have been synthesized using a simple, hydrothermal method and used as a catalyst for ORR. Shape dependent electroactivity is demonstrated by comparing the activity of TiC-NW with its bulk counterparts. Comparative studies reveal higher ORR activities in the case of 1D TiC-NW involving similar to 4 electrons showing efficient reduction of molecular oxygen. Excellent stability and high methanol tolerance with good selectivity for ORR is reported.

A multifold reduction in the transition Reynolds number, and ultra-fast mixing, in a micro-channel due to a dynamical instability induced by a soft wall

A dynamical instability is observed in experimental studies on micro-channels of rectangular cross-section with smallest dimension 100 and 160 mu m in which one of the walls is made of soft gel. There is a spontaneous transition from an ordered, laminar flow to a chaotic and highly mixed flow state when the Reynolds number increases beyond a critical value. The critical Reynolds number, which decreases as the elasticity modulus of the soft wall is reduced, is as low as 200 for the softest wall used here (in contrast to 1200 for a rigid-walled channel) The instability onset is observed by the breakup of a dye-stream introduced in the centre of the micro-channel, as well as the onset of wall oscillations due to laser scattering from fluorescent beads embedded in the wall of the channel. The mixing time across a channel of width 1.5 mm, measured by dye-stream and outlet conductance experiments, is smaller by a factor of 10(5) than that for a laminar flow. The increased mixing rate comes at very little cost, because the pressure drop (energy requirement to drive the flow) increases continuously and modestly at transition. The deformed shape is reconstructed numerically, and computational fluid dynamics (CFD) simulations are carried out to obtain the pressure gradient and the velocity fields for different flow rates. The pressure difference across the channel predicted by simulations is in agreement with the experiments (within experimental errors) for flow rates where the dye stream is laminar, but the experimental pressure difference is higher than the simulation prediction after dye-stream breakup. A linear stability analysis is carried out using the parallel-flow approximation, in which the wall is modelled as a neo-Hookean elastic solid, and the simulation results for the mean velocity and pressure gradient from the CFD simulations are used as inputs. The stability analysis accurately predicts the Reynolds number (based on flow rate) at which an instability is observed in the dye stream, and it also predicts that the instability first takes place at the downstream converging section of the channel, and not at the upstream diverging section. The stability analysis also indicates that the destabilization is due to the modification of the flow and the local pressure gradient due to the wall deformation; if we assume a parabolic velocity profile with the pressure gradient given by the plane Poiseuille law, the flow is always found to be stable.

Instantaneous reduction of graphene oxide at room temperature

We report an environment friendly and green approach to obtain few-layer graphene by the almost instantaneous reduction of graphene oxide using Mg ribbons in acidic solution with a hydrogen spillover mechanism. The typical time is 1-5 min, which is much faster than the reduction by other metal catalysts.

Experimental determination and activity coefficient based models for mixture solubilities of nitrophenol isomers in supercritical carbon dioxide

The experimental solubilities of the mixture of nitrophenol (m- and p-) isomers were determined at 308, 318 and 328 K over a pressure range of 10-17.55 MPa. Compared to the binary solubilities, the ternary solubilities of m-nitrophenol increased at 308, 318 and 328 K. The ternary solubilities of p-nitrophenol increased at 308 K, while the ternary solubilities decreased at lower pressures and increased at higher pressure at 318 and 328 K. The solubilities of the solid mixtures in supercritical carbon dioxide (SCCO2) were correlated with solution models by incorporating the non-idealities using activity coefficient based models. The Wilson and NRTL activity coefficient models were applied to determine the nature of the interactions between the molecules. The equation developed by using the NRTL model has three parameters and correlates mixture solubilities of solid solutes in terms of temperature and cosolute composition. The equation derived from the Wilson model contains five parameters and correlates solubilities in terms of temperature, density and cosolute composition. These two new equations developed in this work were used to correlate the solubilities of 25 binary solid mixtures including the current data. The average AARDs of the model equations derived using the NRTL and Wilson models for the solid mixtures were found to be 7% and 4%, respectively. (C) 2012 Elsevier B.V. All rights reserved.

A strategy-proof and budget-balanced mechanism for carbon footprint reduction by global companies

The problem addressed in this paper is concerned with an important issue faced by any green aware global company to keep its emissions within a prescribed cap. The specific problem is to allocate carbon reductions to its different divisions and supply chain partners in achieving a required target of reductions in its carbon reduction program. The problem becomes a challenging one since the divisions and supply chain partners, being autonomous, may exhibit strategic behavior. We use a standard mechanism design approach to solve this problem. While designing a mechanism for the emission reduction allocation problem, the key properties that need to be satisfied are dominant strategy incentive compatibility (DSIC) (also called strategy-proofness), strict budget balance (SBB), and allocative efficiency (AE). Mechanism design theory has shown that it is not possible to achieve the above three properties simultaneously. In the literature, a mechanism that satisfies DSIC and AE has recently been proposed in this context, keeping the budget imbalance minimal. Motivated by the observation that SBB is an important requirement, in this paper, we propose a mechanism that satisfies DSIC and SBB with slight compromise in allocative efficiency. Our experimentation with a stylized case study shows that the proposed mechanism performs satisfactorily and provides an attractive alternative mechanism for carbon footprint reduction by global companies.